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US6288232B2 - Synthesis of pyrazolinylnaphthalic acid derivatives - Google Patents

Synthesis of pyrazolinylnaphthalic acid derivatives Download PDF

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US6288232B2
US6288232B2 US09/740,983 US74098300A US6288232B2 US 6288232 B2 US6288232 B2 US 6288232B2 US 74098300 A US74098300 A US 74098300A US 6288232 B2 US6288232 B2 US 6288232B2
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acetylnaphthalic
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Victor M. Shershukov
Valentina T. Skripkina
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
    • C07D403/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
    • C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
    • C07D471/06—Peri-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B57/00—Other synthetic dyes of known constitution
    • C09B57/08—Naphthalimide dyes; Phthalimide dyes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B57/00—Other synthetic dyes of known constitution
    • C09B57/12—Perinones, i.e. naphthoylene-aryl-imidazoles

Definitions

  • the invention relates to a method for preparing derivatives of the pyrazolinylnaphthalic acid having the general formula
  • Ar 1 and Ar 2 are unsubstituted or substituted phenyl radicals bearing in the para position an alkylated or acylated oxy- or amino group, or a polynuclear aryl radical;
  • Ar 3 is a substituted N-naphthalimid or 1,8-naphthylene-1′,2′-benzimidazole.
  • R 1 is a unsubstituted or substituted aromatic or heterocyclic radical
  • R 2 is a unsubstituted or substituted aromatic radical
  • R 3 is an alkyl, aryl, alkoxy, or halogen.
  • Compounds of this general formula are organic luminophors with emission in the orange-red and red range of the visible spectrum.
  • the above-mentioned compounds are prepared proceeding from condensation products of 4-acetylnaphthalic anhydride with unsubstituted or substituted o-phenylene diamine in glacial acetic acid.
  • the yellowish green crystals formed are filtered off and recrystallized from acetic acid.
  • the acetyl derivative of 1,8-naphthylene-1′,2′-benzimidazole obtained is treated with aromatic or heterocyclic aldehyde in ethanol in the presence of sodium hydroxide, stirred at ambient temperature, and diluted with water.
  • the precipitate formed is separated by filtration and recrystallized from acetic acid. An unsaturated ketone is obtained.
  • ketone is treated with phenyl hydrazine or its substitute in glacial acetic acid under reflux, the crystals precipitated from the cooled solution are filtered off, washed with methanol, and dried.
  • the product is obtained as water-insoluble red or dark-red crystals soluble in conventional organic solvents.
  • the ready (commercial grade) product yield is from 62 to 85%.
  • R 1 and R 2 are unsubstituted or substituted aromatic radicals.
  • Compounds of this structure are organic luminophors with orange, orange-red, and red emission.
  • the method consists of a first synthesis stage, in which a mixture of 4-acetylnaphthalic anhydride, aniline, and glacial acetic acid is heated under reflux, the reaction mixture is cooled, the precipitated gray crystals are separated by filtration, treated with hydrochloric acid solution, then with hot sodium carbonate solution, and recrystallized from acetic acid. Acetyl derivative, the 4-acetylnaphthalic acid phenylimide is obtained.
  • the acetyl derivative the 4-acetylnaphthalic acid phenylimide
  • the acetyl derivative is converted into an unsaturated ketone.
  • 4-acetylnaphthalic acid phenylimide, ethanol, sodium hydroxide solution, and benzaldehyde are stirred at ambient temperature.
  • the precipitate formed is separated by filtration, water washed till neutral reaction (litmus), dried, and re-crystallized from toluene.
  • the product is obtained as yellow crystals.
  • the unsaturated ketone is treated with phenyl hydrazine in a mixture of ethanol and sodium hydroxide solution under reflux.
  • the crystals precipitated from the mixture under cooling are separated by filtration, water washed till neutral reaction, and treated with boiling alcohol.
  • the product obtained is purified using chromatography of toluene solution.
  • the final product is obtained as red crystals at yield of 57 to 64%.
  • Another method is known for preparing luminophors of the structure and emission region similar to the subject of this application; the method consists in that 4-cinnamoyl-1,8-naphthylene-1′,2′-benzimidazole is condensed with o-tolyl hydrazine in acetic acid medium under boiling, i.e., similar to the methods described above. The precipitate formed is separated by filtration, dried, and purified by the column chromatography. By this method, 4-[1-(2-methylphenyl)-5-phenyl-2-pyrazolinyl-3]-1,8-naphthoylene-1′,2′-benzimidazole with the structure shown is obtained.
  • the use of the method of the present invention will permit the synthesis of the named luminophores to be carried out faster with a higher yield of the product. That will eliminate the extra cost related to the use of chemicals and labor and will provide for the more economical synthesis of the product.
  • Ar 1 and Ar 2 are unsubstituted or substituted phenyl radicals bearing in the para position an alkylated or acylated oxy or amino group, or a polynuclear aryl radical;
  • Ar 3 is a substituted N-naphthalimid or 1,8-naphthylene-1′,2′-benzimidazole.
  • Ar 1 and Ar 2 are unsubstituted or substituted phenyl radicals bearing in the para position an alkylated or acylated oxy- or amino group, or a polynuclear aryl radical;
  • Ar 3 is a substituted N-naphthalimid or 1,8-naphthylene-1′,2′-benzimidazole.
  • the object of this invention is to develop a method for preparing pyrazolinylnaphthalic acid derivatives of general formula
  • Ar 1 and Ar 2 are unsubstituted or substituted phenyl radicals bearing an alkylated or acylated oxy- or amino group in the para position, or a polynuclear aryl radical;
  • Ar 3 is a substituted N-naphthalimid or 1,8-naphthylene-1′,2′-benzimidazole.
  • the method of the present invention permits, by way of a novel change in the synthetic steps and conditions and simplification of the synthesis, reducing its labor requirements, and enhancing the final product yield and quality (purity grade).
  • the previously known method includes the reaction of 4-acetylnaphthalic anhydride with organic reagents by way of a series of successive transformations resulting in formation of the corresponding ketone, treating of the latter with phenyl hydrazine or substituted phenyl hydrazine under heating in a solvent, and separation of the final product by filtration.
  • the initial 4-acetylnaphthalic anhydride is first reacted with the corresponding aromatic or heterocyclic aldehyde in aqueous alkali medium, the formed disodium salt of cinnamoylnaphthalic acid is condensed with a substituted or unsubstituted aromatic amine obtaining the corresponding ketone and then with phenyl hydrazine, and the formed final product is separated.
  • the disodium cinamoyl naphthoate is the common intermediate in the synthesis of red range luminophors.
  • its interaction with aniline gives phenylimide of 4-cinnamoylnaphthalic acid while with o-phenylene diamine, 4(5)-cinnamoyl-1,8-naphthoylene-1′,2′-benzimidazole is obtained. This allows one to avoid the synthesis of specific intermediates for each color range, thus simplifying the process substantially.
  • a mixture of disodium 4-cinnamoyl naphthoate (15.79 g), aniline (4.89 g), and acetic acid (60 ml ) is boiled for 6 h.
  • the reaction mixture is cooled down to room temperature (20° C.).
  • the precipitate is separated by filtration and washed with water and hot alcohol.
  • the compound is prepared and purified as described in Example 1.
  • the initial products 4-acetylnaphthalic anhydride (10.8 g), anisaldehyde (6.12 g), aniline (4.89 g), and phenyl hydrazine (4.1 g).
  • the product is obtained as dark-red crystals, m.p. 215° C., insoluble in water, soluble in usual organic solvents. Yield: 12.13 g (80%).
  • Luminescence (toluene): ⁇ max 575 nm.
  • the compound is prepared and purified as described in Example 1.
  • the initial products 4-acetylnaphthalic anhydride (21.6 g), benzaldehyde (9.54 g), p-anizidine (13 g), and phenyl hydrazine (10.3 g).
  • the final product yield is 83%.
  • the product is obtained as red crystals, m.p. 268° C., insoluble in water, soluble in usual organic solvents.
  • Luminescence (toluene): ⁇ max 570 nm.
  • the compound is prepared and purified as described in Example 1.
  • the initial products 4-acetylnaphthalic anhydride (10.8 g), anisaldehyde (6.12 g), aniline (4.89 g), and 2-naphthyl phenyl hydrazine (7.48 g).
  • the product is obtained as dark-red crystals, m.p. 202-205° C., insoluble in water, soluble in usual organic solvents. Yield: 15.66 g (75%).
  • Luminescence (toluene): ⁇ max 617 nm.
  • the compound is prepared and purified as described in Example 1.
  • the initial products 4-acetylnaphthalic anhydride (10.8 g), anisaldehyde (6.12 g), aniline (4.89 g), and 4-carbomethoxyphenyl hydrazine (7.86 g).
  • the product is obtained as orange crystals, m.p. 255-257° C., water-insoluble, soluble in usual organic solvents. Yield: 17.15 g (81%).
  • Luminescence (toluene): ⁇ max 570 nm.
  • the compound is prepared and purified as described in Example 1.
  • the initial products 4-acetylnaphthalic anhydride (10.8 g), benzaldehyde (5.25 g), o-phenylene diamine (5.68 g), and phenyl hydrazine (4.43 g).
  • the product is obtained as red crystals, m.p. 262-263° C., insoluble in water, soluble in usual organic solvents.
  • Luminescence (toluene): ⁇ max 598 nm.
  • the compound is prepared and purified as described in Example 1.
  • the initial products 4-acetylnaphthalic anhydride (10.8 g), anisaldehyde (6.12 g), o-phenylene diamine (5.68 g), and phenyl hydrazine (4.6 g).
  • the final product yield from 14.1 g of corresponding unsaturated ketone: 13.98 g (82%).
  • the product is obtained as red crystals, m.p. 242-243° C., insoluble in water, soluble in usual organic solvents.
  • Luminescence (toluene): ⁇ max 600 nm.
  • the compound is prepared and purified as described in Example 1.
  • the initial products 4-acetylnaphthalic anhydride (10.8 g), furfan-2-aldehyde (5.25 g), o-phenylene diamine (5.68 g), and phenyl hydrazine (4.4 g).
  • the product is obtained as dark-brown crystals, m.p. 251-252° C., insoluble in water, soluble in usual organic solvents. Yield: 10.35 g (75%).
  • Luminescence (toluene): ⁇ max 595 nm.
  • the compound is prepared and purified as described in Example 1.
  • the initial products 4-acetylnaphthalic anhydride (10.8 g), 4-dimethylaminobenzaldehyde (5.25 g), o-phenylene diamine (5 g), and phenyl hydrazine (3.78 g).
  • the final product yield from 11.95 g of corresponding unsaturated compound: 11.5 g (80%).
  • the product is obtained as red crystals, m.p. 256-258° C., insoluble in water, soluble in usual organic solvents.
  • Luminescence (toluene): ⁇ max 610 nm.
  • the compound is prepared and purified as described in Example 1.
  • the initial products 4-acetylnaphthalic anhydride (10.8 g), anisaldehyde (6.12 g), o-naphthylene diamine (8.31 g), and phenyl hydrazine (4.54 g).
  • the product is obtained as red crystals, m.p. 238-240° C., insoluble in water,, soluble in usual organic solvents. Yield: 14.4 g (78%).
  • Luminescence (toluene): ⁇ max 604 nm.
  • the method of the present invention develops a novel technologic method for preparing pyrazolinylnaphthalic acid being orange, orange-red, and red range luminophors.
  • the method is simplified and more convenient as compared to known methods due to that, first, disodium salt of cinnamoylnaphthalic acid is a common intermediate in the synthesis of luminophors having all necessary emission colors, so there is no need for preparation of acetyl derivative specific for each color range and, second, there is no need for intermediates purification at each synthesis stage. This reduces considerably the production cost and labor consumption.
  • the final product is essentially free of impurities, thus, its quality is improved. Since the losses at the intermediate process stages are reduced (due to the chromatographic purification is unnecessary), the yield of final pure products is enhanced up to 80% in contrast to 50% according to previously known methods.
  • the semi-industrial scale technology has been developed for preparing of products with various emission colors.

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  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Plural Heterocyclic Compounds (AREA)

Abstract

The invention pertains to a method for preparing derivatives of the pyrazolinylnaphthalic acid having the general formulawhere Ar1 and Ar2 are unsubstituted or substituted phenyl radicals bearing in the para position an alkylated or acylated oxy- or amino group, or a polynuclear aryl radical, and Ar3 is a substituted N-naphthalimid or 1,8-naphthylene-1',2'-benzimidazole. Compounds of the above general formula are high-efficient red organic luminophors and are used widely as luminescent components of dyes for plastics and liquid scintillators, in hydrogeology to study water streams, to label the chemical industry wastewaters, as laser dyes, etc.

Description

CROSS REFERENCE TO RELATED PATENT APPLICATIONS
This application is related to and claims priority on Ukrainian patent application serial number 99127167, filed Dec. 28, 1999.
FIELD OF THE INVENTION
The invention relates to a method for preparing derivatives of the pyrazolinylnaphthalic acid having the general formula
Figure US06288232-20010911-C00002
where
Ar1 and Ar2 are unsubstituted or substituted phenyl radicals bearing in the para position an alkylated or acylated oxy- or amino group, or a polynuclear aryl radical; and
Ar3 is a substituted N-naphthalimid or 1,8-naphthylene-1′,2′-benzimidazole.
BACKGROUND OF THE INVENTION
A method is known (see Ref.1—USSR Author's Certificate No. 179,324, Cl. C09d) for preparing derivatives of pyrazolinylnaphthalic acid having the general formula
Figure US06288232-20010911-C00003
where
R1 is a unsubstituted or substituted aromatic or heterocyclic radical;
R2 is a unsubstituted or substituted aromatic radical;
R3 is an alkyl, aryl, alkoxy, or halogen.
Compounds of this general formula are organic luminophors with emission in the orange-red and red range of the visible spectrum.
The above-mentioned compounds are prepared proceeding from condensation products of 4-acetylnaphthalic anhydride with unsubstituted or substituted o-phenylene diamine in glacial acetic acid. The yellowish green crystals formed are filtered off and recrystallized from acetic acid. The acetyl derivative of 1,8-naphthylene-1′,2′-benzimidazole obtained is treated with aromatic or heterocyclic aldehyde in ethanol in the presence of sodium hydroxide, stirred at ambient temperature, and diluted with water. The precipitate formed is separated by filtration and recrystallized from acetic acid. An unsaturated ketone is obtained. The ketone is treated with phenyl hydrazine or its substitute in glacial acetic acid under reflux, the crystals precipitated from the cooled solution are filtered off, washed with methanol, and dried. The product is obtained as water-insoluble red or dark-red crystals soluble in conventional organic solvents. The ready (commercial grade) product yield is from 62 to 85%. Luminescence characteristics: in toluene, λmax=598 to 610 nm; in crystal form, λmax=620 to 670 nm.
Another method has been also described (see Ref.2—USSR Author's Certificate No. 196,873, Cl. C09d) for preparing derivatives of pyrazolinylnaphthalic acid having general formula
Figure US06288232-20010911-C00004
where
R1 and R2 are unsubstituted or substituted aromatic radicals. Compounds of this structure are organic luminophors with orange, orange-red, and red emission.
The method consists of a first synthesis stage, in which a mixture of 4-acetylnaphthalic anhydride, aniline, and glacial acetic acid is heated under reflux, the reaction mixture is cooled, the precipitated gray crystals are separated by filtration, treated with hydrochloric acid solution, then with hot sodium carbonate solution, and recrystallized from acetic acid. Acetyl derivative, the 4-acetylnaphthalic acid phenylimide is obtained.
At the second stage, the acetyl derivative, the 4-acetylnaphthalic acid phenylimide, is converted into an unsaturated ketone. To that end, 4-acetylnaphthalic acid phenylimide, ethanol, sodium hydroxide solution, and benzaldehyde are stirred at ambient temperature. The precipitate formed is separated by filtration, water washed till neutral reaction (litmus), dried, and re-crystallized from toluene. The product is obtained as yellow crystals.
At the third synthesis stage, the unsaturated ketone is treated with phenyl hydrazine in a mixture of ethanol and sodium hydroxide solution under reflux. The crystals precipitated from the mixture under cooling are separated by filtration, water washed till neutral reaction, and treated with boiling alcohol. The product obtained is purified using chromatography of toluene solution. The final product is obtained as red crystals at yield of 57 to 64%. The crystals are water-insoluble and soluble in organic solvents. Luminescence: in toluene, λmax=570 nm.
The methods for preparing luminophors disclosed in the above-mentioned Author's Certificates are almost identical with each other except for that 4-acetylnaphthalic anhydride is treated with aniline to obtain orange-red luminophors (Ref.2) while to produce red ones, the same anhydride is reacted with o-phenylene diamine.
In this reaction, the same drawbacks are typical of both methods, namely:
(A) Low quality of the final product. The product contains considerable amounts of impurities, mainly unsaturated naphthalic acid derivatives that cause green fluorescence. The presence of such impurities in the final product is due to the preparation method itself. The final product purification from the impurities mentioned is associated with difficulties in the process, increased production costs, and substantial losses of the final product. To obtain high-quality luminophors, the chromatographic purification is required resulting in a loss of 30 to 40% of the final product. In Ref.2 the yields of various red range luminophors are said to be from 62 to 85%. The real useful product yield after the purification is, however, only from 35 to 50%.
(B) The process is difficult to perform and laborious. When producing orange, orange-red, and red luminophors, the corresponding intermediates, i.e., acetyl derivatives, are to be prepared every time. For example, 4-acetylnaphthalic anhydride is to be condensed with aniline preparing 4-acetylnaphthalic acid phenylimide to produce luminophors emitting in orange range, while to obtain red luminophors, the same anhydride must be condensed with o-phenylene diamine preparing 4(5)-acetyl-1,8-naphthoylene-1′,2′-benzimidazole. These preparations make the process difficult and increase its cost.
(C) Moreover, the process is complicated by the purification of intermediates both at the stages of their synthesis and at the preparation of final products.
Another method is known for preparing luminophors of the structure and emission region similar to the subject of this application; the method consists in that 4-cinnamoyl-1,8-naphthylene-1′,2′-benzimidazole is condensed with o-tolyl hydrazine in acetic acid medium under boiling, i.e., similar to the methods described above. The precipitate formed is separated by filtration, dried, and purified by the column chromatography. By this method, 4-[1-(2-methylphenyl)-5-phenyl-2-pyrazolinyl-3]-1,8-naphthoylene-1′,2′-benzimidazole with the structure shown is obtained.
Figure US06288232-20010911-C00005
The luminophore compounds so prepared are fluorescent in the orange-red spectral region with a large Stokes shift: in toluene, absorption at λmax=470 nm, luminescence at λmax=595 nm. (See Ref.3—USSR Author's Certificate No. 1,148,291, Cl. C09K 11/06).
The use of the method of the present invention will permit the synthesis of the named luminophores to be carried out faster with a higher yield of the product. That will eliminate the extra cost related to the use of chemicals and labor and will provide for the more economical synthesis of the product.
REFERENCES
1. B. M. Krasovitskiy and E. A. Shevchenko “Method of preparation of organic luminophores”, USSR Authors Certificate (A.C.) #179324, c09d, B. I, 5 (1966).
2. B. M. Krasovitskiy, E. G. Yushko, and D. G. Pereyaslova “Method of preparation of organic luminophores”, USSR Authors Certificate (A.C.) #196873, c09d, B. I, 2 (1967).
3. V. M. Shershukov, B. M. Krasovitskiy and T. A. Shehovtsova “4-[1-(2-methylphenyl)-5-phenyl-2-pirazolynil-3]-1′,8′-naphthoylen-1′,2′-benzimidazole as an orange-red luminophore”, USSR Authors Certificate (A.C.) #1148291, c09k, 11/06, B. I, 47-48 (1993).
The USSR Authors Certificate is an equivalent of a patent that has been filed in the USSR only.
OBJECTS OF THE INVENTION
It is therefore an object of the present invention to develop a method for preparing pyrazolinylnaphthalic acid derivatives of the general formula
Figure US06288232-20010911-C00006
where
Ar1 and Ar2 are unsubstituted or substituted phenyl radicals bearing in the para position an alkylated or acylated oxy or amino group, or a polynuclear aryl radical; and
Ar3 is a substituted N-naphthalimid or 1,8-naphthylene-1′,2′-benzimidazole.
It is another object of the present invention to provide a method to simplify and reduce the time it takes to synthesize the above compounds.
It is a further object of the present invention to enhance the final product yield and quality (purity grade) of the above compounds.
Additional objects and advantages of the invention are set forth, in part, in the description which follows and, in part, will be apparent to one of ordinary skill in the art from the description and/or from the practice of the invention.
SUMMARY OF THE INVENTION
In response to the foregoing challenge, Applicants have developed an innovative, economical method for preparing derivatives of the pyrazolinylnaphthalic acid having the general formula
Figure US06288232-20010911-C00007
where
Ar1 and Ar2 are unsubstituted or substituted phenyl radicals bearing in the para position an alkylated or acylated oxy- or amino group, or a polynuclear aryl radical; and
Ar3 is a substituted N-naphthalimid or 1,8-naphthylene-1′,2′-benzimidazole.
It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only, and are not restrictive of the invention as claimed. The accompanying drawings, which are incorporated herein by reference, and which constitute a part of this specification, illustrate certain embodiments of the invention, and together with the detailed description serve to explain the principles of the present invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
Reference will now be made in detail to a preferred embodiment of the present invention, an example of which is illustrated in the accompanying examples.
The object of this invention is to develop a method for preparing pyrazolinylnaphthalic acid derivatives of general formula
Figure US06288232-20010911-C00008
where
Ar1 and Ar2 are unsubstituted or substituted phenyl radicals bearing an alkylated or acylated oxy- or amino group in the para position, or a polynuclear aryl radical; and
Ar3 is a substituted N-naphthalimid or 1,8-naphthylene-1′,2′-benzimidazole.
The method of the present invention permits, by way of a novel change in the synthetic steps and conditions and simplification of the synthesis, reducing its labor requirements, and enhancing the final product yield and quality (purity grade).
This object is attained by the following. The previously known method includes the reaction of 4-acetylnaphthalic anhydride with organic reagents by way of a series of successive transformations resulting in formation of the corresponding ketone, treating of the latter with phenyl hydrazine or substituted phenyl hydrazine under heating in a solvent, and separation of the final product by filtration.
According to the present invention, the initial 4-acetylnaphthalic anhydride is first reacted with the corresponding aromatic or heterocyclic aldehyde in aqueous alkali medium, the formed disodium salt of cinnamoylnaphthalic acid is condensed with a substituted or unsubstituted aromatic amine obtaining the corresponding ketone and then with phenyl hydrazine, and the formed final product is separated.
The novel modification of the process and the modified stages and synthesis conditions, namely, reacting 4-acetylnaphthalic anhydride not with aromatic amine but with aromatic aldehyde makes it possible to exclude from the process the unsubstituted naphthalic acid comprised in the anhydride in considerable amounts as an impurity. Under the newly developed reaction mode, the unsubstituted acid does not interact chemically with the aromatic aldehyde (in contrast to the amine in the previously known method) and is removed from the reaction mixture as a solution of its sodium salt in the course of filtration of the formed disodium cinnamoyl naphthoate that is essentially insoluble in the aqueous alkali reaction medium.
In this reaction, a considerable amount of by-products are eliminated at the consecutive condensation of cinnamoylnaphhalic acid with aromatic amine. Moreover, the disodium cinamoyl naphthoate is the common intermediate in the synthesis of red range luminophors. For example, its interaction with aniline gives phenylimide of 4-cinnamoylnaphthalic acid while with o-phenylene diamine, 4(5)-cinnamoyl-1,8-naphthoylene-1′,2′-benzimidazole is obtained. This allows one to avoid the synthesis of specific intermediates for each color range, thus simplifying the process substantially.
The method of the present invention is realized according to the following scheme:
Figure US06288232-20010911-C00009
The process stages are as follows:
Treating 4-acetylnaphthalic anhydride with corresponding aldehyde in aqueous alkali medium to obtain disodium salt of 4-cinnamoylnaphthalic acid.
Treating the of 4-cinnamoylnaphthalic acid salt with corresponding mono- or diamine obtaining <<chalcone>>.
Interaction of the obtained <<chalcone>> with phenyl hydrazine or its substituted derivative in a solvent.
Separation of the formed final product from the reaction mixture by filtration.
Purification of the product by chromatography.
Some specific examples of the invention embodiments are presented below.
EXAMPLE 1 Preparation of 4-(1,5-diphenyl-2-pyrazolin-3-yl)-N-phenyl naphthalimide
A mixture of 4-acetylnaphthalic anhydride (10.8 g) (prepared by acenaphthene acylation with acetic anhydride in the presence of anhydrous zinc chloride with the consecutive oxidation of the formed acetyl acenaphthene with sodium dichromate), benzaldehyde (5.25 g), and 4.4% sodium hydroxide solution (120 ml) is stirred for 4 h at room temperature. The precipitate of disodium 4-cinnamoyl naphthoate is separated by filtration and washed with alcohol. A mixture of disodium 4-cinnamoyl naphthoate (15.79 g), aniline (4.89 g), and acetic acid (60 ml ) is boiled for 6 h. The reaction mixture is cooled down to room temperature (20° C.). The precipitate is separated by filtration and washed with water and hot alcohol. A mixture of 4-cinnamoyl-N-phenyl naphthalimide (12.1 g), phenyl hydrazine (4.26 g), ethanol (100 ml), and 10% alkali solution (6 ml) is boiled for 6 h, cooled down to 20° C., the precipitate is separated by filtration, washed with water and alcohol, and purified by chromatography on aluminum oxide eluting with chloroform/tetrachloromethane (1:1). The product is obtained as red crystals, m.p. 221-223° C., water-insoluble, soluble in usual organic solvents. Yield: 11.24 g (75%). Luminescence (toluene): λmax=570 nm.
EXAMPLE 2 Preparation of 4-[(1-phenyl-5-(4-methoxyphenyl)-2-pyrazolin-3-yl]-N-phenyl naphthalimide
The compound is prepared and purified as described in Example 1. The initial products: 4-acetylnaphthalic anhydride (10.8 g), anisaldehyde (6.12 g), aniline (4.89 g), and phenyl hydrazine (4.1 g). The product is obtained as dark-red crystals, m.p. 215° C., insoluble in water, soluble in usual organic solvents. Yield: 12.13 g (80%). Luminescence (toluene): λmax=575 nm.
EXAMPLE 3 Preparation of 4-[(1,5-diphenyl-2-pyrazolin-3-yl)]-N-(4-methoxyphenyl) naphthalimide
The compound is prepared and purified as described in Example 1. The initial products: 4-acetylnaphthalic anhydride (21.6 g), benzaldehyde (9.54 g), p-anizidine (13 g), and phenyl hydrazine (10.3 g). The final product yield is 83%. The product is obtained as red crystals, m.p. 268° C., insoluble in water, soluble in usual organic solvents. Luminescence (toluene): λmax=570 nm.
EXAMPLE 4 Preparation of 4-[1(2-naphthyl)-5-(4-methoxyphenyl)-2-pyrazolin-3-yl]-N-phenyl naphthalimide
The compound is prepared and purified as described in Example 1. The initial products: 4-acetylnaphthalic anhydride (10.8 g), anisaldehyde (6.12 g), aniline (4.89 g), and 2-naphthyl phenyl hydrazine (7.48 g). The product is obtained as dark-red crystals, m.p. 202-205° C., insoluble in water, soluble in usual organic solvents. Yield: 15.66 g (75%). Luminescence (toluene): λmax=617 nm.
EXAMPLE 5 Preparation of 4-[(1-(4-carbomethoxyphenyl)-5-(4-methoxyphenyl-2-pyrazolin-3-yl)]-N-phenyl naphthalimide
The compound is prepared and purified as described in Example 1. The initial products: 4-acetylnaphthalic anhydride (10.8 g), anisaldehyde (6.12 g), aniline (4.89 g), and 4-carbomethoxyphenyl hydrazine (7.86 g). The product is obtained as orange crystals, m.p. 255-257° C., water-insoluble, soluble in usual organic solvents. Yield: 17.15 g (81%). Luminescence (toluene): λmax=570 nm.
EXAMPLE 6 Preparation of 1,5-diphenyl-3-(1,8-naphthoylene-1′,2′-benzimidazol-4-yl)-2-pyrazoline
The compound is prepared and purified as described in Example 1. The initial products: 4-acetylnaphthalic anhydride (10.8 g), benzaldehyde (5.25 g), o-phenylene diamine (5.68 g), and phenyl hydrazine (4.43 g). The product is obtained as red crystals, m.p. 262-263° C., insoluble in water, soluble in usual organic solvents. Luminescence (toluene): λmax=598 nm.
EXAMPLE 7 Preparation of 1-phenyl-5-(4-methoxyphenyl)-3-(1,8-naphthoylene-1′,2′-benzimidazol-4-yl)-2-pyrazoline
The compound is prepared and purified as described in Example 1. The initial products: 4-acetylnaphthalic anhydride (10.8 g), anisaldehyde (6.12 g), o-phenylene diamine (5.68 g), and phenyl hydrazine (4.6 g). The final product yield from 14.1 g of corresponding unsaturated ketone: 13.98 g (82%). The product is obtained as red crystals, m.p. 242-243° C., insoluble in water, soluble in usual organic solvents. Luminescence (toluene): λmax=600 nm.
EXAMPLE 8 Preparation of 1-phenyl-5-furyl-3-(1,8-naphthoylene-1′,2′-benzimidazol-4-yl)-2-pyrazoline
The compound is prepared and purified as described in Example 1. The initial products: 4-acetylnaphthalic anhydride (10.8 g), furfan-2-aldehyde (5.25 g), o-phenylene diamine (5.68 g), and phenyl hydrazine (4.4 g). The product is obtained as dark-brown crystals, m.p. 251-252° C., insoluble in water, soluble in usual organic solvents. Yield: 10.35 g (75%). Luminescence (toluene): λmax=595 nm.
EXAMPLE 9 Preparation of 1-phenyl-5-(4-dimethylaininophenyl)-3-(1,8-naphthoylene-1′,2′-benzimidazol-4-yl)-2-pyrazoline
The compound is prepared and purified as described in Example 1. The initial products: 4-acetylnaphthalic anhydride (10.8 g), 4-dimethylaminobenzaldehyde (5.25 g), o-phenylene diamine (5 g), and phenyl hydrazine (3.78 g). The final product yield from 11.95 g of corresponding unsaturated compound: 11.5 g (80%).The product is obtained as red crystals, m.p. 256-258° C., insoluble in water, soluble in usual organic solvents. Luminescence (toluene): λmax=610 nm.
EXAMPLE 10 Preparation of 1-phenyl-5-(4-methoxyphenyl)-3-(1,8-naphthoylene-1′,2′-benzimidazol-4-yl)-2-pyrazoline
The compound is prepared and purified as described in Example 1. The initial products: 4-acetylnaphthalic anhydride (10.8 g), anisaldehyde (6.12 g), o-naphthylene diamine (8.31 g), and phenyl hydrazine (4.54 g). The product is obtained as red crystals, m.p. 238-240° C., insoluble in water,, soluble in usual organic solvents. Yield: 14.4 g (78%). Luminescence (toluene): λmax=604 nm.
It is seen from the description and the examples that the method of the present invention develops a novel technologic method for preparing pyrazolinylnaphthalic acid being orange, orange-red, and red range luminophors. The method is simplified and more convenient as compared to known methods due to that, first, disodium salt of cinnamoylnaphthalic acid is a common intermediate in the synthesis of luminophors having all necessary emission colors, so there is no need for preparation of acetyl derivative specific for each color range and, second, there is no need for intermediates purification at each synthesis stage. This reduces considerably the production cost and labor consumption.
Due to the improvements mentioned above, the final product is essentially free of impurities, thus, its quality is improved. Since the losses at the intermediate process stages are reduced (due to the chromatographic purification is unnecessary), the yield of final pure products is enhanced up to 80% in contrast to 50% according to previously known methods. At present, the semi-industrial scale technology has been developed for preparing of products with various emission colors.
It will be apparent to those skilled in the art that various modifications and variations can be made in the construction, configuration, and/or operation of the present invention without departing from the scope or spirit of the invention. For example, in the embodiments mentioned above, various changes may be made to the synthesis or reagents without departing from the scope and spirit of the invention. Further, it may be appropriate to make additional modifications or changes to the reaction conditions without departing from the scope of the invention. Thus, it is intended that the present invention cover the modifications and variations of the invention provided they come within the scope of the appended claims and their equivalents.

Claims (45)

We claim:
1. A method for preparing a compound of formula I
Figure US06288232-20010911-C00010
wherein Ar1 and Ar2 are each independently selected from the group consisting of an unsubstituted phenyl radical, a phenyl radical substituted at the para position with an alkoxy group, an acyloxy group, an alkylamino group or an acylamino group, a naphthyl radical and a polynuclear aromatic radical; and Ar3 is selected from the group consisting of
Figure US06288232-20010911-C00011
wherein X and Y are each independently selected from the group consisting of hydrogen, an alkoxy group, an acyloxy group, an alkylamino group and an acylamino group;
said method comprising the steps of:
(a) reacting 4-acetylnaphthalic anhydride (II)
Figure US06288232-20010911-C00012
 with an aldehyde of formula III
Figure US06288232-20010911-C00013
 in the presence of an aqueous base to form a compound of formula IV:
Figure US06288232-20010911-C00014
(b) boiling the compound of formula IV in the presence of either a compound of formula V:
Figure US06288232-20010911-C00015
or a compound of formula VI:
Figure US06288232-20010911-C00016
 to form a compound of formula VII:
Figure US06288232-20010911-C00017
(c) boiling the compound of formula VII in the presence of a compound of formula VIII:
Figure US06288232-20010911-C00018
in the presence of ethanol in a 10% alkali solution.
2. A method for preparing a compound of formula I
Figure US06288232-20010911-C00019
wherein Ar1 and Ar2 are each independently selected from the group consisting of an unsubstituted phenyl radical, a phenyl radical substituted at the para position with an alkoxy group, an acyloxy group, an alkylamino group or an acylamino group, a naphthyl radical and a polynuclear aromatic radical, and X is selected from the group consisting of hydrogen, an alkoxy group, an acyloxy group, an alkylamino group and an acylamino group;
said method comprising the steps of:
(a) reacting 4-acetylnaphthalic anhydride (II)
Figure US06288232-20010911-C00020
 with an aldehyde of formula III
Figure US06288232-20010911-C00021
 in the presence of an aqueous base to form a compound of formula IV:
Figure US06288232-20010911-C00022
(b) boiling the compound of formula IV in the presence of a compound of formula V:
Figure US06288232-20010911-C00023
 to form a compound of formula VI:
Figure US06288232-20010911-C00024
(c) boiling the compound of formula VI in the presence of a compound of formula VII:
Figure US06288232-20010911-C00025
in the presence of ethanol in a 10% alkali solution.
3. A method for preparing a compound of formula I
Figure US06288232-20010911-C00026
wherein Ar1 and Ar2 are each independently selected from the group consisting of an unsubstituted phenyl radical, a phenyl radical substituted at the para position with an alkoxy group, an acyloxy group, an alkylamino group or an acylamino group, a naphthyl radical and a polynuclear aromatic radical, and Y is selected from the group consisting of hydrogen, an alkoxy group, an acyloxy group, an alkylamino group and an acylamino group;
said method comprising the steps of:
(a) reacting 4-acetylnaphthalic anhydride (II)
Figure US06288232-20010911-C00027
 with an aldehyde of formula III
Figure US06288232-20010911-C00028
 in the presence of an aqueous base to form a compound of formula IV:
Figure US06288232-20010911-C00029
(b) boiling the compound of formula IV in the presence of a compound of formula V:
Figure US06288232-20010911-C00030
 to form a compound of formula VI:
Figure US06288232-20010911-C00031
(c) boiling the compound of formula VI in the presence of a compound of formula VII:
Figure US06288232-20010911-C00032
in the presence of ethanol in a 10% alkali solution.
4. The method of claim 1, wherein Ar3 is:
Figure US06288232-20010911-C00033
5. The method of claim 3, wherein Y is hydrogen.
6. The method of claim 1, wherein Ar3 is:
Figure US06288232-20010911-C00034
7. The method of claim 2, wherein X is hydrogen.
8. The method of claim 1, wherein Ar3 is:
Figure US06288232-20010911-C00035
9. The method of claim 2, wherein X is a methoxy group.
10. The method of claim 1, wherein Ar1 and Ar2 are each
Figure US06288232-20010911-C00036
11. The method of claim 2, wherein Ar1 and Ar2 are each
Figure US06288232-20010911-C00037
12. The method of claim 3, wherein Ar1 and Ar2 are each
Figure US06288232-20010911-C00038
13. The method of claim 1, wherein Ar1 is
Figure US06288232-20010911-C00039
14. The method of claim 2, wherein Ar1 is
Figure US06288232-20010911-C00040
15. The method of claim 3, wherein Ar1 is
Figure US06288232-20010911-C00041
16. The method of claim 1, wherein Ar2 is
Figure US06288232-20010911-C00042
17. The method of claim 2, wherein Ar2 is
Figure US06288232-20010911-C00043
18. The method of claim 1, wherein Ar2 is
Figure US06288232-20010911-C00044
19. The method of claim 2, wherein Ar2 is
Figure US06288232-20010911-C00045
20. The method of claim 1, wherein Ar1 is
Figure US06288232-20010911-C00046
21. The method of claim 3, wherein Ar1 is
Figure US06288232-20010911-C00047
22. The method of claim 1, wherein Ar1 is
Figure US06288232-20010911-C00048
23. The method of claim 3, wherein Ar1 is
Figure US06288232-20010911-C00049
24. The method of claim 1, wherein said 4-acetylnaphthalic anhydride is reacted with said aldehyde of formula III for about 4 hours.
25. The method of claim 2, wherein said 4-acetylnaphthalic anhydride is reacted with said aldehyde of formula III for about 4 hours.
26. The method of claim 3, wherein said 4-acetylnaphthalic anhydride is reacted with said aldehyde of formula III for about 4 hours.
27. The method of claim 1, wherein said compound of formula IV is boiled in the presence of either said compound of formula V or said compound of formula VI for about 6 hours.
28. The method of claim 2, wherein said compound of formula IV is boiled in the presence of said compound of formula V for about 6 hours.
29. The method of claim 3, wherein said compound of formula IV is boiled in the presence of said compound of formula V for about 6 hours.
30. The method of claim 1, wherein said compound of formula VII is boiled in the presence of said compound of formula VIII for about 6 hours.
31. The method of claim 2, wherein said compound of formula VI is boiled in the presence of said compound of formula VII for about 6 hours.
32. The method of claim 3, wherein said compound of formula VI is boiled in the presence of said compound of formula VII for about 6 hours.
33. The method of claim 1, wherein said aqueous base in step (a) is sodium hydroxide.
34. The method of claim 2, wherein said aqueous base in step (a) is sodium hydroxide.
35. The method of claim 3, wherein said aqueous base in step (a) is sodium hydroxide.
36. A method for preparing the compound of formula I
Figure US06288232-20010911-C00050
said method comprising the steps of:
(a) reacting 4-acetylnaphthalic anhydride (II)
Figure US06288232-20010911-C00051
 with benzaldehyde (III)
Figure US06288232-20010911-C00052
 in the presence of aqueous sodium hydroxide to form 4-cinnamoyl naphthoate (IV):
Figure US06288232-20010911-C00053
(b) boiling 4-cinnamoyl naphthoate (IV) in the presence of aniline (V):
Figure US06288232-20010911-C00054
 to form the compound of formula VI:
Figure US06288232-20010911-C00055
 and
(c) boiling the compound of formula VI in the presence of phenylhydrazine (VII)
Figure US06288232-20010911-C00056
in the presence of ethanol in a 10% alkali solution.
37. A method for preparing the compound of formula I
Figure US06288232-20010911-C00057
said method comprising the steps of:
(a) reacting 4-acetylnaphthalic anhydride (II)
Figure US06288232-20010911-C00058
 with anisaldehyde (III)
Figure US06288232-20010911-C00059
 in the presence of aqueous sodium hydroxide to form the compound of formula IV:
Figure US06288232-20010911-C00060
(b) boiling the compound of formula IV in the presence of aniline (V):
Figure US06288232-20010911-C00061
 to form the compound of formula VI:
Figure US06288232-20010911-C00062
(c) boiling the compound of formula VI in the presence of phenylhydrazine (VII)
Figure US06288232-20010911-C00063
 in the presence of ethanol in a 10% alkali solution.
38. A method for preparing the compound of formula I
Figure US06288232-20010911-C00064
said method comprising the steps of:
(a) reacting 4-acetylnaphthalic anhydride (II)
Figure US06288232-20010911-C00065
 with benzaldehyde (III)
Figure US06288232-20010911-C00066
 in the presence of aqueous sodium hydroxide to form the compound of formula IV:
Figure US06288232-20010911-C00067
(b) boiling the compound of formula IV in the presence of p-anidizine (V):
Figure US06288232-20010911-C00068
 to form the compound of formula VI:
Figure US06288232-20010911-C00069
(c) boiling the compound of formula VI in the presence of phenylhydrazine (VII)
Figure US06288232-20010911-C00070
in the presence of ethanol in a 10% alkali solution.
39. A method for preparing the compound of formula I
Figure US06288232-20010911-C00071
said method comprising the steps of:
(a) reacting 4-acetylnaphthalic anhydride (II)
Figure US06288232-20010911-C00072
 with anisaldehyde (III)
Figure US06288232-20010911-C00073
 in the presence of aqueous sodium hydroxide to form the compound of formula IV:
Figure US06288232-20010911-C00074
(b) boiling the compound of formula IV in the presence of aniline (V):
Figure US06288232-20010911-C00075
 to form the compound of formula VI:
Figure US06288232-20010911-C00076
 and
(c) boiling the compound of formula VI in the presence of 2-naphthylphenylhydrazine (VII)
Figure US06288232-20010911-C00077
in the presence of ethanol in a 10% alkali solution.
40. A method for preparing the compound of formula I
Figure US06288232-20010911-C00078
said method comprising the steps of:
(a) reacting 4-acetylnaphthalic anhydride (II)
Figure US06288232-20010911-C00079
 with anisaldehyde (III)
Figure US06288232-20010911-C00080
 in the presence of aqueous sodium hydroxide to form the compound of formula IV:
Figure US06288232-20010911-C00081
(b) boiling the compound of formula IV in the presence of aniline (V):
Figure US06288232-20010911-C00082
 to form the compound of formula VI:
Figure US06288232-20010911-C00083
 and
(c) boiling the compound of formula VI in the presence of 4-carbomethoxyphenylhydrazine (VII)
Figure US06288232-20010911-C00084
in the presence of ethanol in a 10% alkali solution.
41. A method for preparing the compound of formula I
Figure US06288232-20010911-C00085
said method comprising the steps of:
(a) reacting 4-acetylnaphthalic anhydride (II)
Figure US06288232-20010911-C00086
 with benzaldehyde (III)
Figure US06288232-20010911-C00087
 in the presence of aqueous sodium hydroxide to form the compound of formula IV:
Figure US06288232-20010911-C00088
(b) boiling the compound of formula IV in the presence of o-phenylene diamine (V):
Figure US06288232-20010911-C00089
 to form the compound of formula VI:
Figure US06288232-20010911-C00090
 and
(c) boiling the compound of formula VI in the presence of phenylhydrazine (VII):
Figure US06288232-20010911-C00091
in the presence of ethanol in a 10% alkali solution.
42. A method for preparing the compound of formula I
Figure US06288232-20010911-C00092
said method comprising the steps of:
(a) reacting 4-acetylnaphthalic anhydride (II)
Figure US06288232-20010911-C00093
 with anisaldehyde (III)
Figure US06288232-20010911-C00094
 in the presence of aqueous sodium hydroxide to form the compound of formula IV:
Figure US06288232-20010911-C00095
(b) boiling the compound of formula IV in the presence of o-phenylene diamine (V):
Figure US06288232-20010911-C00096
 to form the compound of formula VI:
Figure US06288232-20010911-C00097
 and
(c) boiling the compound of formula VI in the presence of phenyl hydrazine (VIl):
Figure US06288232-20010911-C00098
in the presence of ethanol in a 10% alkali solution.
43. A method for preparing the compound of formula I
Figure US06288232-20010911-C00099
said method comprising the steps of:
(a) reacting 4-acetylnaphthalic anhydride (II)
Figure US06288232-20010911-C00100
 with furan-2-aldehyde (III)
Figure US06288232-20010911-C00101
 in the presence of aqueous sodium hydroxide to form the compound of formula IV:
Figure US06288232-20010911-C00102
(b) boiling the compound of formula IV in the presence of o-phenylene diamine (V):
Figure US06288232-20010911-C00103
 to form the compound of formula VI:
Figure US06288232-20010911-C00104
 and
(c) boiling the compound of formula VI in the presence of phenylhydrazine (VII):
Figure US06288232-20010911-C00105
in the presence of ethanol in a 10% alkali solution.
44. A method for preparing the compound of formula I
Figure US06288232-20010911-C00106
said method comprising the steps of:
(a) reacting 4-acetylnaphthalic anhydride (II)
Figure US06288232-20010911-C00107
 with 4-N,N-dimethylaminobenzaldehyde (III)
Figure US06288232-20010911-C00108
 in the presence of aqueous sodium hydroxide to form the compound of formula IV:
Figure US06288232-20010911-C00109
(b) boiling the compound of formula IV in the presence of o-phenylene diamine (V):
Figure US06288232-20010911-C00110
 to form the compound of formula VI:
Figure US06288232-20010911-C00111
 and
(c) boiling the compound of formula VI in the presence of phenylhydrazine (VII):
Figure US06288232-20010911-C00112
in the presence of ethanol in a 10% alkali solution.
45. A method for preparing the compound of formula I
Figure US06288232-20010911-C00113
said method comprising the steps of:
(a) reacting 4-acetylnaphthalic anhydride (II)
Figure US06288232-20010911-C00114
 with anisaldehyde (III)
Figure US06288232-20010911-C00115
 in the presence of aqueous sodium hydroxide to form the compound of formula IV:
Figure US06288232-20010911-C00116
(b) boiling the compound of formula IV in the presence of o-phenylene diamine (V):
Figure US06288232-20010911-C00117
 to form the compound of formula VI:
Figure US06288232-20010911-C00118
 and
(c) boiling the compound of formula VI in the presence of phenylhydrazine (VII):
Figure US06288232-20010911-C00119
in the presence of ethanol in a 10% alkali solution.
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US20050025992A1 (en) * 2001-08-21 2005-02-03 Andreas Richter Organic electroluminescent device based on 2,5-diaminoterephthalic acid derivatives
US7112674B2 (en) 2001-08-21 2006-09-26 Sensient Imaging Technologies Gmbh Organic electroluminescent device based on 2,5-diaminoterephthalic acid derivatives
US7141312B2 (en) 2001-08-21 2006-11-28 Sensient Imaging Technologies Gmbh Organic electroluminescent device based on 2,5-diaminoterephthalic acid derivatives
US20100314556A1 (en) * 2008-01-31 2010-12-16 Commissariat A L'energie Atomique Et Aux Energies Alternatives 1,8-naphthalimide derivatives as scintillation agents, in particular for discriminating between fast neutrons and gamma rays
US8894881B2 (en) * 2008-01-31 2014-11-25 Commissariat A L'energie Atomique Et Aux Energies Alternatives 1,8-naphthalimide derivatives as scintillation agents, in particular for discriminating between fast neutrons and gamma rays
CN102295601A (en) * 2011-05-18 2011-12-28 东南大学 Arylpyrazoline luminescent compounds with 5-position substituted by polycyclic aromatic hydrocarbon

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